Polymers from piperylene concentrates



y 3, 1956 5. P. HAMNER POLYMERS FROM PIPERYLENE CONCENTRATES Filed Dec.1, 1952 Glen P. Ham ner inventor Bv Clttorneg United States PatentOffice 2,753,382 Patented July 3, 1956 POLYMERS FROM PIPERYLENE CON CENTRATES This invention is concerned with the preparation of polymer oilsfrom piperylene containing fractions boiling between IOU-150 F. obtainedas selected distillate cuts from steam cracked petroleum streams.

In general, heavier petroleum fractions such as naphtha, gas oil, andthe like, are cracked at relatively low pressure and at temperatures of1000 to 1500 F. in the presence of steam and for relatively shortcontact times. The gas and liquid streams produced contain largequantities of diolefins and olefins in the C to C range.

A naphtha produced by steam cracking contains large amounts ofdiolefins, olefins, aromatics, and some paraffins. The C5 fraction(64-115 F.) from such a naphtha contains -20 wt. percent isoprene, 10-15wt. percent cyclopentadiene, 10-15 wt. percent piperylene, 5 wt. percentother diolefins, 15-20 wt. percent tertiary olefins, 25 wt. percentnormal olefins, and 2-5 wt. percent paratfins.

By using an initial, mild thermal soaking of the C5 fraction containingolefins, diolefins, cyclic diolefins and aromatics at a temperature of100-250" F. and suflicient treating time, the cyclopentadienes aredimerized and are removed as the dimers from the bottom of adistillation tower. This tower is operated to prevent any substantialdepolymerization of the cyclodienes. The overhead, consisting of theundimerized portion, contains chiefly olefins and diolefins andaromatics, including the isoprene. Isoprene is recovered from the 60-100F. fraction by extractive distillation. The remaining C5 fraction (100-115" F.) from isoprene extraction feed preparation contains 40-50 wt.percent cis and trans piperylene, cyclopentane, l-methyl-l-cyclo-butene,trimethylethylene, l-2 pentadiene, 2-methyl-1-2-butadiene, and smallamount of a Ca olefin (t-butylethylene) A polymerization of the reactivecomponents in this stream is carried out in the presence of boronfluoride as a polymerization catalyst. This comprises a method forpreparing polymerized oils of good quality. Under controlled conditions,good polymerization activity of the reactive aliphatic olefins anddiolefins is obtained.

The above piperylene polymer oils can be used as drying oils or they canbe copolymerized with other resins for paint or varnish manufacture orformulated in printing ink. The polymers have good color and odor. Thepiperylene polymers may be modified by the addition of other materialsto the feed before polymerization with BFs.

Using BFa as the polymerization catalyst, temperatures in the range of20 F. to +40 F. are preferred. An inert diluent, such as a hydrocarbonnaphtha or hexane or heptane may be used if desired.

The polymerization reaction is carried out as a liquid phase operation.The catalyst may be added continually or batchwise. Any practical andefiective methods for adding catalyst and reagents can be utilized. Whenthe catalyst used is gaseous boron fluoride, the liquid materialundergoing reaction must be well agitated to insure adequate saturationof the liquid with the gas.

2 EXAMPLE 1 A selected steam cracked distillate stream was subjected toa thermal treatment to dimeri-ze the cyclodienes. These cyclodienedimers were then removed by careful fractionation as a bottoms stream.The lighter portions were obtained as an overhead stream. This overheadstream was substantially freed of isoprene by selective fractionationand extraction of this component. The bottoms fraction recovered fromthe fractionation step was useful as feed for this process. It containsfrom 40m 50 wt. percent of cis and trans piperylene. A typical analysisof the 100-115 F. fraction thus obtained is as follows:

Component Analysis 1 Analysis 2 Isoprene, wt., percent 1. 1 1. 5t-penetene 2, w't., percent 3.6 c-pentene-2, wt., percent 7. 4 22. 7 2Methyl butene-2, u. percent 13.7 Oyclopentadiene, Wt., percent" s(approx.) 1. 2 1. 2 t-piperylene, wt., percent 34. 2 52 5 c-piperylene,wt., percent. 20. 9 Cyclopentene, wt., percent 14. 7 19. 4'Cyclopentane, Wt., percent 1. 5 Acetylene as pentyne-l, .wt percent 0.7 06+, wt., percent 1.0 2.4 Refractive Index, 12,9 1. 4183 SpecificGravity, 20/4? 0 0. 6926 Conjugated Dienes by maleic anhydride,

wt., percent 45.1

The above fraction (100-115" F. boiling range) containing piperylene waspolymerized with BF: gas with a yield of approximately wt. percentpolymer. The polymerization was carried out at 30 to 40 F. Results ofthis reaction are shown in Table I.

A similar fraction as used in Example 1 above F.) containing piperlyenewas polymerized with BFa gas with a yield of 75.4 wt. percent polymer.The feed was first diluted in a A ratio with a virgin naphtha as diluentand treated at LOO- F. for 15 minutes residence time before addition ofalcohol and Water to destroy the catalyst. The unreacted portion and thevirgin naphtha was removed by distillation. Results of this reaction areshown in Table II.

Table II Polymer properties:

Iodine number (ASTM) 302 Color:

Gardner 9 Gardner, dil. 1 Viscosity, SSU 210 F 65 Gravity, API 60 F 26.7NVM, wt. percent:

3 hrs 32.8 24 hrs 77.5

1 1 gm. polymer/67 mls. xylene.

3 EXAMPLE 3 Polymer oils prepared from a piperylene concentrate stream,as described in Example 1, were tested as raw materials in varnishcompositions. The liquid resin was pentanized naphtha is removed fromtower A as stream 3, with part returned by line 17 to the tower tosupply heat required during the distillation. Stream 2 is thermallysoaked in drum B for 6l6 hours at 220 F. to

cooked with vegetable drying oils including both linseed 5 dimerizCyclopentadlene, The thermal Soaked oil and mug The mug n formulationappears to stream 18 is fed to toweg C having 20 plates and operated besomewhat better. The liquid resin was readily inwlth a and 240 top andbottoms temperature corporated into the varnish. The resulting varnishesrespectively and at pounds pressure. The overhead were satisfactory asto color, viscosity, and air drying rate. Stream 4 contams lsoprene andPlperylene and olefins- The baked fihcontaining the polymer Wenespecially 10 Stream returns reflux to tower C. Streanr 5 1s bottomsgood. Results of the testing of the varnishes are shown Stream fromlower C Where the cyclopentadlfine dlIf'lel' 18 in Tables III and IV,removed from the other C5 components. A part is re- The varnishescontained 0.4% lead and 0.04% marigaturned to the tower by line 19.Stream 4 is fed to tower nese drier based on the polymer. The oil lengthvalue is 15 D having 50 plates and operated at 100 F. and 114 F.expressed in terms of gallons of oil per hundred pounds top and bottomstemperature, respectively, and at 15-20 of resin. pounds pressure.Stream 6 containing the isoprene (final Table III Cooking Gardner ValuesDrying Rate (Hrs.) Varnish Oil No. Oil Length Temp., Time. Percent ColorViscosity 1 2 4 6 24 48 F. Hrs. Loss (poise) 1 Linseed.-. 15 560 s 31.713 2.0 8 8 7 5 0 0 2 ung 15 450 2 13.0 9 0.5 8 7 5 3. 2 1

1 Drying rate code: 9wet; 7film just clings to finger; 6-set to touch;3decided tack but dust free; 0tack ree.

1 Evaluation code: Hard (Sward) in percent based on plate glass as 100.

Chemical resistance: 0unafiected; 1-3whitened'or discolored and. lessadhesion; 4-6-softened and loss in adhesion; 79-pinholed or hlistered tofailure by removal of the film.

Flexibility (180 bend test): 0u.naficcted; 1-4hazed and less adhesion;5-6fine cracking; 79-heavy cracking and peeling.

"The low hardness exhibited in this test is a reflection of the highloss of resin during cooking.

EXAMPLE 4 Similar comparative tests were conducted by the preparation ofvarnishes from a solid hydrocarbon resin having a 76 C. melting point.This resin had been prepared by polymerizing a piperylene containing cutboiling up to 60 C. using AlCla as the polymerizing catalyst. This resinwas not readily soluble in the conjugated oils (tung and oiticica) andgave the general appearance of very poor incompatibility with them.

It is thus seen that AlCl3 polymerized resins are not as satisfactory asvarnish constituents as are the polymer oils prepared by BF3 catalyst,when these piperylene containing fractions are employed as thepolymerization feed streams.

EXAMPLE 5 The invention will be understood in greater detail by thefollowing explanation which is to be read in conjunction with theaccompanying schematic figure.

A debutanized steam cracked distillate containing C5, C6, and C1components is fed as stream 1 to tower A, having plates and operatedwith 200 F. top temperature and 350 F. bottoms temperature at 45-50 lbs.pressure. Stream 2 is a concentrated C fraction (final boiling point 145F.) taken as an overhead stream and fed to a thermal soaking drum B.Part of stream 2 is returned as liquid reflux by line 16 to tower A. Thedeboiling point F.) and low boiling C5 olefins is taken as an overheadstream to be fed to a diolefin extraction unit for isoprene recovery, ifdesired. Stream 21 is a reflux stream to the tower. Stream 7 containingthe piperylene (100-115" F.) and heavier boiling olefins is removed as abottoms stream to be polymerized with a Friedel-Crafts type catalystsuch as BE; in reactor E. An inert diluent is introduced through line 8with the piperylene concentrate fed to reactor E. The reactor isoperated at 150 F., preferably 050 F. or lower. Agitation is provided bystirrer 25. The catalyst is introduced continuously through line 15. Thecatalyst may be BF3 gas or its complexes. The polymerized feed andsolvent stream 10 is fed to vessel F for water or steam washing.Agitation is provided by stirrer 26. The catalyst is removed with thewater through line 12. The solvent and polymerized material is then fedto tower G by line 11. Tower G has 30 plates and is operated with 120 F.top and 400 F. bottom temperature. Stream 9 is side stream or recyclesolvent. Stream 13 contains the unreacted C5 fraction, mostlytrimethylethylene and cyclopentene. Reflux to the tower is provided byline 24. The piperylene polymer is removed from the bottom of tower Gthrough line 14. Heat is supplied to the column by return line 23. Toimprove the polymer color, stream 11 may be charcoal treated prior todistillation to remove small amounts of color present.

What is claimed is:

1. A process for the preparation of polymer products which comprisessubjecting a steam cracked petroleum fraction boiling between 100 and F.and consisting of 40 weight percent up to 50 weight percent piperyleneand 50 to 60% of a mixture of cyclopentanes, l-methylcyclobutene,tri-methyleneethylene, 1,2-pentadiene, 2- methyl-l-Z-butadiene, andtertiary butyl ethylene to polymerization in the presence of BF at atemperature in the range of -20 F. to +40 F.

2. A process for the preparation of unsaturated polymer oils whichcomprises treating a steam cracked petroleum stream boiling between 100and 115 F. and consisting of 40 to 50 weight percent of piperylene and50 to 60% of a mixture of cyclopentanes, l-methyl-cyclobutene,tri-methyleneethylene, 1,2-pentadiene, Z-methyl- I-Z-butadiene andtertiary butyl ethylene with BB at a temperature below 0 F.

3. An unsaturated drying oil prepared by the polymerization of a steamcracked petroleum fraction boiling from 100 to 115 F. and consisting of40% to 50% piperylene and 50 to 60% of a mixture of cyclopentanes,l-methylcyclobutene, tri-methylethylene, 1,2-pentadiene, 2-methyl- 5ride catalyst at a temperature between 20 and +40 F.

I-Z-butadiene and tertiary butyl ethylene in the presence of BFa as apolymerization catalyst.

4. A process for the preparation of polymer products which comprisessubjecting a steam cracked fraction boiling at 64 to 115 F. andcontaining 15 to 20 weight percent of isoprene, 1Q to 15 weight percentof cyclopentadiene, to weight percent of piperylene, 5 weight percent ofother diolefins, 15 to weight percent fortiary olefins, 20 to weightpercent normal olefins and 2 to 5% normal paraflins to a thermal soakingat a temperature of IOU-250 F. until the cyclopentadienes are 1dimerized, distilling the dimerized fraction to remove thedicyclopentadienes, distilling the dicyclopentadiene-free fraction toremove isoprene and subjecting the remaining fraction to polymerizationin the presence of boron fluo- References Cited in the file of thispatent UNITED STATES PATENTS Mikeska et al Sept. 14, 1937 2,131,195Schneider et al. Sept. 27, 1938 2,151,382 Harmon Mar. 21, 1939 2,252,333Rothrock Aug. 12, 1941 2,704,778 Maisel Mar. 22, 1955

4. A PROCESS FOR THE PREPARATION OF POLYMER PRODUCTS WHICH COMPRISESSUBJECTING A STEAM CRACKED FRACTION BOILING AT 64 TO 115* F. ANDCONTAINING 15 TO 20 WEIGHT PERCENT OF ISOPRENE, 10 AND 15 WEIGHT PERCENTOF CYCLOPENTADIENE, 10 TO 15 WEIGHT PERCENT OF PIPERYLENE, 5 WEIGHTPERCENT OF OTHER DIOLEFINS, 15 TO 20 WEIGHT PERCENT TERTIARY OLEFINS, 20TO 25 WEIGHT PERCENT NORMAL OLEFINS AND 2 TO 5% NORMAL PARAFFINS TO ATHERMAL SOAKING AT A TEM-